US8343627B2 - Core-shell nanoparticles with multiple cores and a method for fabricating them - Google Patents
Core-shell nanoparticles with multiple cores and a method for fabricating them Download PDFInfo
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- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
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- G01N33/543—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals
- G01N33/551—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals the carrier being inorganic
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Definitions
- the present invention relates to core-shell nanoparticles with multiple cores and a method for fabricating them.
- Nanoparticles exhibit intriguing changes in electronic, optical, and magnetic properties as a result of the nanoscale dimensionality (Daniel et al., Chem. Rev. 104:293 (2004); Xia et al., Adv. Mater. 12:693 (2000)).
- the ability to engineer size and monodispersity is essential for the exploration of these properties.
- the preparation of magnetic nanoparticles and nanocomposites has attracted both fundamental and practical interest because of potential applications in areas such as ferrofluids, medical imaging, drug targeting and delivery, cancer therapy, separations, and catalysis (Kim et al., J. Magn. Magn. Mater. 225:256 (2001); Niemeyer, Angew. Chem. Int. Ed.
- the present invention is directed to overcoming these deficiencies in the art.
- One aspect of the present invention is directed toward core-shell nanoparticles, each comprising a ligand-capped metal shell surrounding a plurality of discrete, nonconcentric, metal-containing cores.
- Another aspect is directed to a method of producing core-shell nanoparticles, each comprising a ligand-capped metal shell surrounding one or more metal-containing cores.
- This method includes providing ligand-capped metal-containing core material nanoparticles and ligand-capped metal shell material nanoparticles. These nanoparticles are reacted under conditions effective to produce the core-shell nanoparticles comprising a ligand-capped metal shell surrounding one or more metal-containing cores.
- a further aspect of the present invention is directed to a method of separating a target molecule from a sample.
- core-shell nanoparticles each comprising a ligand-capped metal shell surrounding a plurality of discrete, nonconcentric, metal-containing cores are provided, with a first binding material bound to the ligand-capped shell.
- the binding material that specifically binds to the target molecule is incubated with the sample in a reaction vessel under conditions effective for the first binding material to bind to the target molecule.
- the reaction vessel is contacted with a magnet under conditions effective to immobilize the nanoparticles in the reaction vessel.
- the immobilized nanoparticles may be recovered.
- Disclosed herein is a novel thermal approach to the fabrication of core-shell magnetic nanoparticles with not only high monodispersity but also size tunability in the 5-100 nm range.
- the basic idea explores the viability of hetero-interparticle coalescence between gold and magnetic nanoparticles under encapsulating environment for creating core-shell type nanoparticles in which the magnetic core consists of single or multiple metal cores with a pomegranate-like interior structure depending on the degree of coalescence (see FIG. 1 ).
- This approach is new and differs from previous methods for synthesizing gold-coated Fe-Oxide particles in two significant ways: First, the present method uses a thermal evolution method starting from Fe-Oxide nanoparticles and Au nanoparticles as precursors, whereas the previous synthesis method uses Fe-Oxide nanoparticles and Au(Ac) 3 molecules as precursors. Second, the present method produces golden magnetic particles with either single core or multiple cores, whereas the previous method produces golden magnetic particles with only a single core.
- FIG. 1 is a schematic drawing illustrating the hetero-interparticle coalescence of nanoparticles.
- Component 1 A represents ligand-capped metal shell material nanoparticles.
- Component 1 B represents ligand-capped metal-containing core material nanoparticles.
- Component A and B combine to form nanoparticles (i.e. Component C) comprising a ligand-capped metal shell surrounding a single metal-containing core.
- Component C coalesces to form component D which is a nanoparticle comprising a ligand-capped metal shell surrounding a plurality of discrete, nonconcentric, metal-containing cores.
- FIG. 2A shows a schematic drawing of a core-shell nanoparticle with binding material and antibodies bound to the core-shell nanoparticle.
- FIG. 2B-C are schematic drawings of methods of concentrating target analytes using magnetic nanoparticles.
- FIGS. 3A-B are TEM micrographs of gold nanoparticles produced by thermal processing (149° C.) of Au 2nm -DT nanoparticles.
- FIG. 3A shows the precursor nanoparticles 2.0 ⁇ 0.4 nm and
- FIG. 3B shows the product nanoparticles (6.4 ⁇ 0.4 nm).
- FIGS. 4A-B are TEM images of OA/OAM-capped Fe 2 O 3 nanoparticles produced by thermal processing (149° C.): before ( FIG. 4A , 4.4 ⁇ 0.3 nm) and after ( FIG. 4B , 4.5 ⁇ 0.5 nm) thermal processing.
- FIGS. 5A-C are TEM images for precursor Fe 2 O 3 ( FIG. 5A ), Au ( FIG. 5B ), and thermally-evolved Au-coated Fe 2 O 3 nanoparticles using 25:1 ratio of Au to Fe 2 O 3 nanoparticles ( FIG. 5C ).
- FIG. 8 is a schematic illustration of the dithiolate-gold based binding chemistry for the thin film assembly of Fe 2 O 3 @Au (A), Au (B) and Fe 2 O 3 (C) nanoparticles on a substrate.
- FIGS. 9A-B are SERS spectra for MBA label which are incorporated onto OA-OAM capped Fe 2 O 3 @Au nanoparticles ( FIG. 9A ) and protein-A capped Au nanoparticles ( FIG. 9B ).
- FIGS. 10A-C is a photograph showing magnetic properties of Fe 2 O 3 @Au nanoparticles dissolved in toluene ( FIG. 1A ), suspended in ethanol-toluene ( FIG. 10B ), and after applying a magnet to the suspension of FIG. 10B ( FIG. 10C ).
- FIGS. 11A-B are FTIR spectra of OA/OM-capped core@shell Fe 2 O 3 @Au particles before ( FIG. 11A ) and after ( FIG. 11B ) ligand exchange reaction with MUA.
- FIG. 12 is an illustration of the reactions and product separation of antibody-labeled Fe 2 O 3 @Au nanoparticles in two different reaction systems: (A1-B1): reaction with protein A capped gold nanoparticles, and (A2-B2): reaction with BSA capped gold nanoparticles.
- A1-B1 reaction with protein A capped gold nanoparticles
- A2-B2 reaction with BSA capped gold nanoparticles.
- SERS Label L
- MCA mercaptobenzoic acid
- Ab anti-rabbit IgG.
- FIG. 13 is a UV-Vis spectra monitoring the reaction between Au/Protein-A/L and Fe 2 O 3 @Au/Ab (A1).
- Inset the spectra monitoring the reaction between Au/BSA/L and Fe 2 O 3 @Au/Ab (A2).
- the spectra were recorded as a function of time (within 1 hr).
- the arrows indicate the direction of the spectral evolution as a function of time.
- FIG. 14 is a SERS spectra of the products from the reactions between Au/Protein-A/L and Fe 2 O 3 @Au/Ab and between Au/BSA/L and Fe 2 O 3 @Au/Ab (A2).
- a magnet was used to collect the particles, which were then deposited on a Au substrate.
- One aspect of the present invention is directed toward core-shell nanoparticles, each comprising a ligand-capped metal shell surrounding a plurality of discrete, nonconcentric, metal-containing cores.
- the core-shell nanoparticles may be present in a monodispersion with controlled diameters ranging from 5 nm to 100 nm.
- the metal-containing cores may be magnetic, paramagnetic or superparamagnetic.
- the metal of the metal-containing cores may be iron (e.g., Fe 3 O 4 or Fe 2 O 3 ), magnesium, cobalt, or mixtures thereof.
- the metal of the metal shell may be gold, silver, platinum, rhodium, palladium, vanadium, titanium, iron, cobalt, magnesium, ruthenium, chromium, molybdenum, tantalum, zirconium, manganese, tin, or mixtures thereof.
- the capping ligand may be decanethiolate, oleylamine, oleic acid, acrylates, N,N-trimethyl(undecylmercapto)ammonium (TUA), tetrabutylammonium tetrafluoroborate (TBA), tetramethylammonium bromide (TMA), cetyltrimethylammonium bromide (CTAB), citrates, poly methacrylate, ascorbic acid, DNA, 2-mercaptopropionic acid (MPA), 3-mercaptopropionic acid (MPA), 11-mercaptoundecanoic acid (MUA), 10-mercaptodecane-1-sulfonic acid, 16-mercaptohexadecanoic acid, diimide, N-(2-mercaptopropionyl)glycine(tiopronin), 2-mercaptoethanol, 4-mercapto-1-butanol, dodecyl sulfate, amino acids, homocysteine
- the core-shell nanoparticles may further comprise a binding material bound to the ligand-capped shell.
- the binding material may be proteins, peptides, antibodies, or antigens.
- Another aspect is directed to a method of producing core-shell nanoparticles, each comprising a ligand-capped metal shell surrounding one or more metal-containing cores.
- This method includes providing ligand-capped metal-containing core material nanoparticles and ligand-capped metal shell material nanoparticles. These nanoparticles are reacted under conditions effective to produce the core-shell nanoparticles comprising a ligand-capped metal shell surrounding one or more metal-containing cores.
- the method of the present invention provides for hetero-interparticle coalescence of ligand-capped metal shell material nanoparticles, e.g., decanethiolate (DT)-capped Au (Component A) and ligand-capped metal-containing core material nanoparticles, e.g., oleic acid or oleylamine (OA/OM)-capped Fe 2 O 3 (Component B).
- DT decanethiolate
- ligand-capped metal-containing core material nanoparticles e.g., oleic acid or oleylamine (OA/OM)-capped Fe 2 O 3
- Thermal evolution results in the formation of nanoparticles comprising a ligand-capped metal shell surrounding a single metal-containing core (Component C).
- These single-core nanoparticles can undergo further thermal evolution to form nanoparticles comprising a ligand-capped metal shell surrounding a plurality of discrete, nonconcentric, metal-containing cores (Component D).
- the reaction conditions may include combining the ligand-capped metal-containing core material nanoparticles and the ligand-capped metal shell material nanoparticles in a solvent to form a reaction mixture.
- the reaction mixture is heated under conditions effective to form the core-shell nanoparticles comprising a ligand-capped metal shell surrounding one or more metal-containing cores.
- the solvent may include toluene, tetraoctylammonium bromide, and/or decanethiols and may be heated to a temperature of 140-160° C.
- the core-shell nanoparticles may be subjected to one or more sizing operations, such as centrifugation.
- a further aspect of the present invention is directed to a method of separating a target molecule from a sample.
- core-shell nanoparticles each comprising a ligand-capped metal shell surrounding a plurality of discrete, nonconcentric, metal-containing cores are provided, with a first binding material bound to the ligand-capped shell.
- the binding material that specifically binds to the target molecule is incubated with the sample in a reaction vessel under conditions effective for the first binding material to bind to the target molecule.
- the reaction vessel is contacted with a magnet under conditions effective to immobilize the nanoparticles in the reaction vessel.
- the immobilized nanoparticles may be recovered.
- the method may include removing liquids from the reaction vessel. Once the nanoparticles with binding materials are bound to the target in a sample solution and the vessel is contacted with a magnet thereby immobilizing the nanoparticles-target complex, all or some of the sample solution can be removed for further purification, analysis, or other use.
- the liquids can be removed by various means well known in the art including pumping, pouring, pipetting, or evaporation.
- target molecules may be separated from the nanoparticles.
- Target molecules may be reversibly bound to the binding material or the binding material may be reversibly bound to the nanoparticles, allowing separation of the target molecules from the nanoparticles by various methods known in the art such as salvation, exchange, heating, or digestion.
- the binding material may be proteins, peptides, antibodies, antigens or other suitable material known in the art.
- Magnetic separation techniques are commonly used for the purification, quantification, or identification of various substances (see Ito et al., J. Biosci. Bioeng. 100(1): 1-11 (2005); Alexiou et al., J. Nanosci. Nanotechnol., 6:2762 (2006); and Risoen et al., Protein Expr. Purif. 6(3):272-7 (1995), which are hereby incorporated by reference in their entirety).
- the term “magnetic particles” is meant to include particles that are magnetic, paramagnetic, or superparamagnetic properties. Thus, the magnetic particles are magnetically displaceable but are not necessarily permanently magnetizable. Methods for the determination of analytes using magnetic particles are described, for example, in U.S. Pat. No. 4,554,088, which is hereby incorporated by reference in its entirety.
- the magnetic particle may be bound to an affinity ligand, the nature of which will be selected based on its affinity for a particular analyte whose presence or absence in a sample is to be ascertained.
- the affinity molecule may, therefore, comprise any molecule capable of being linked to a magnetic particle which is also capable of specific recognition of a particular analyte.
- Affinity ligands therefore, include monoclonal antibodies, polyclonal antibodies, antibody fragments, nucleic acids, oligonucleotides, proteins, oligopeptides, polysaccharides, sugars, peptides, peptide encoding nucleic acid molecules, antigens, drugs, and other ligands.
- the target material may optionally be a material of biological or synthetic origin.
- target materials may be antibodies, amino acids, proteins, peptides, polypeptides, enzymes, enzyme substrates, hormones, lymphokines, metabolites, antigens, haptens, lectins, avidin, streptavidin, toxins, poisons, environmental pollutants, carbohydrates, oligosaccharides, polysaccharides, glycoproteins, glycolipids, nucleotides, oligonucleotides, nucleic acids and derivatised nucleic acids, DNA, RNA, natural or synthetic drugs, receptors, virus particles, bacterial particles, virus components, cells, cellular components, and natural or synthetic lipid vesicles.
- FIG. 2A shows a representation of antibodies, for example, bound to a magnetic core-shell nanoparticle.
- a magnetic core-shell nanoparticle Such a system could be used to bind a target forming a nanoparticle-target complex.
- Application of a magnetic field will allow immobilization of the nanoparticle-target complex ( FIG. 2B ).
- the nanoparticle-target complex can be concentrated at the site of an assay surface ( FIG. 2C ) allowing for detection or improvement of the limits of detection.
- Magnetic nanoparticles have also been proposed for use in direct sensing methods for diagnosis of cancer (Suzuki et al., Brain Tumor Pathol. 13:127 (1996), which is hereby incorporated by reference in its entirety) and for novel tissue engineering methodologies utilizing magnetic force and functionalized magnetic nanoparticles to manipulate cells (Ito et al., J. Biosci. Bioeng. 100:1-11 (2005), which is hereby incorporated by reference in its entirety).
- a magnetic field may serve to target drug-carrying magnetic particles to a desired body site.
- the dose of systemically administered chemotherapeutics is limited by the toxicity and negative side effects of the drug.
- Therapeutically sufficient concentrations of the drugs in the respective tissues often need to be quite high.
- Magnetic carrier systems should allow targeted drug delivery to achieve such high local concentrations in the targeted tissues, thereby minimizing the general distribution throughout the body.
- Special magnetic guidance systems can direct, accumulate, and hold the particles in the targeted area, for example, a tumor region (Alexiou et al., J. Nanosci. Nanotechnol. 6:2762 (2006), which is hereby incorporated by reference in its entirety).
- Iron pentacarbonyl Fe(CO) 5
- phenyl ether trimethylamine oxide
- decanethiol DT
- TOA-Br decanethiol
- OAM oleylamine
- OA trimethylamine oxide dihydreate
- BSA bovine serum albumin
- UUA 11-mercaptoundecanoic acid
- MSA mercaptobenzoic acid
- DSP dithiobis (succinimidyl propionate)
- solvents hexane, toluene, and ethanol
- Fe 2 O 3 ( ⁇ -Fe 2 O 3 ) nanoparticles and Au nanoparticles were synthesized by known protocols, whereas the preparation of Fe 2 O 3 @Au nanoparticles was based on a new protocol developed in this work.
- Fe 2 O 3 nanoparticles Fe 2 O 3 nanoparticles capped with OA (and/or OAM) were prepared based on the modified procedure reported previously (Wang et al., J. Phys. Chem. B 109:21593 (2005), which is hereby incorporated by reference in its entirety).
- Au nanoparticles For the synthesis of Au nanoparticles, the standard two-phase method reported by House and Schriffrin ( J. Chem. Soc., Chem. Commun. 1994:801-802, which is hereby incorporated by reference in its entirety) was used. Gold nanoparticles of 2 nm diameter encapsulated with DT monolayer shells (Au 2nm -DT) were synthesized.
- the tube was then placed in a preheated Yamato DX400 Gravity Convection Oven at 149° C. for 1-hour. Temperature variation from this set point was limited to ⁇ 1.5° C. After the 1-hour thermal treatment, the reaction tube was allowed to cool down and the particles were redispersed in toluene.
- the above approach can also be used to produce Fe 3 O 4 @Au nanoparticles.
- Fe-oxide was used to refer to a variety of iron oxides, including Fe 2 O 3 and Fe 3 O 4 .
- the as-synthesized DT-capped iron oxide Au particles were transferred to water by ligand exchange using mercaptoundecanoic acid (MUA) by following a procedure reported by Gittins et al. ( Chem. Phys. Chem. 3(1):110-113 (2002), which is hereby incorporated by reference in its entirety), with a slight modification.
- the nanoparticles were further modified with DSP for protein coupling by ligand exchange.
- the nanoparticles were rinsed with centrifuge and 20 ⁇ L of anti-Rabbit IgG (2.4 mg/mL) was pipetted. After overnight incubation, the particles were centrifuged three times and finally resuspended in 2 mM Tris buffer (pH 7.2) with 1% BSA and 0.1% Tween 80. The same method was also used for coating protein A and BSA to Au nanoparticles of 80 nm size. 2.5 ⁇ L of 1 mM DSP was added to 1 mL of Au particles (80 nm, 1 ⁇ 10 10 /mL) and reacted overnight.
- SERS Surface-Enhanced Raman Scattering
- Raman spectra were recorded using the Advantage 200A Raman instrument (DeltaNu).
- the instrument collects data over 200 to 3400 cm ⁇ 1 .
- the laser power was 5 mW and the wavelength of the laser was 632.8 nm.
- the spectrum in the range from 200 to 1500 cm ⁇ 1 was collected.
- TEM micrographs of the particles were obtained using a Hitachi H-7000 Electron Microscope operated at 100 kV.
- the particles dispersed in hexane were drop cast onto a carbon film coated copper grid followed by evaporation at room temperature.
- UV-Vis Ultraviolet-Visible Spectroscopy
- UV-Vis spectra were acquired with a HP8453 spectrophotometer. The spectra were collected over the range of 200-1100 nm.
- DCP-AES Direct Current Plasma-Atomic Emission Spectroscopy
- the composition of synthesized particles and thin films was analyzed using DCP-AES. Measurements were made on emission peaks at 267.59 nm and 259.94 nm, for Au and Fe, respectively.
- the nanoparticle samples were dissolved in concentrated aqua regia, and then diluted to concentrations in the range of 1 to 50 ppm for analysis.
- Calibration curves were constructed from standards with concentrations from 0 to 50 ppm in the same acid matrix as the unknowns. Detection limits, based on three standard deviations of the background intensity are 0.008 ppm and 0.005 ppm for Au and Fe, respectively. Standards and unknowns were analyzed 10 times each for 3 second counts. Instrument reproducibility, for concentrations greater than 100 times the detection limit, results in ⁇ 2% error.
- 3A-B show the representative set of TEM images for gold nanoparticles thermally processed from 2-nm sized, DT-capped gold nanoparticles (2.0 ⁇ 0.4 nm).
- the increased particle size and the high monodispersity of the resulting nanoparticles (6.4 ⁇ 0.4 nm) are consistent with what has been previously reported, demonstrating the effectiveness of the thermal processing condition for processing gold nanoparticles.
- FIGS. 4A-B show a representative set of TEM images for Fe 2 O 3 nanoparticles by thermally processing of Fe 2 O 3 nanoparticles of 4.4 nm size.
- the observation of insignificant changes in the particle size and the monodispersity of the resulting nanoparticles (4.5 ⁇ 0.5 nm) demonstrate the absence of any size evolution for Fe 2 O 3 nanoparticles with the thermal processing conditions used in the present work.
- the absence of size evolution is likely associated with the lack of significant change in melting temperature for Fe 2 O 3 nanoparticles. In other words, Fe 2 O 3 nanoparticles are stable under the thermal processing temperature.
- a toluene solution of the two precursor nanoparticles e.g., stock solutions of decanethiolate (DT)-capped Au (2 nm, 158 ⁇ M) and OAM and/or OA-capped Fe 2 O 3 (5 nm, 6.3 ⁇ M), or Fe 3 O 4 with a controlled ratio in a reaction tube was heated in an oven at 149° C. for 1 hour.
- Other constituents in the solution included TOA-Br and DT with controlled concentrations. After cooling to room temperature, the solidified liquid was dispersable in toluene.
- FIGS. 5A-C show a representative set of TEM micrographs comparing the resulting nanoparticles obtained from the thermal processing treatment with the two precursor nanoparticles.
- the observed features appear to correspond to the early stage of coalescence of the core-shell nanoparticles.
- the thermal evolution in a larger reaction volume spherical clusters with highly ordered packing morphology were observed ( FIG. 7D ).
- the center of the spherical assembly shows indications of interparticle coalescence, in contrast to the loosely-bound nanoparticles spread around the spherical outline.
- Control experiments showed that under the temperature while Au nanoparticles could be evolved to sizes of up to 10 nm, Fe 2 O 3 nanoparticles remained unchanged. Thus, these large-sized particles likely consist of multiple Fe-oxide cores.
- the first question concerns whether surface of the nanoparticles are composed of Au shell, and the second question concerns whether the nanoparticle cores include magnetic Fe 2 O 3 nanoparticles.
- HRTEM high-resolution TEM
- ED electron diffraction
- the resulting nanoparticles include the desired Au shell
- two types of measurements were carried out, both of which were based on the surface chemistry of gold-thiolate binding and core-shell composition.
- the core-shell composition was analyzed, for which samples were prepared by assembling the nanoparticles into thin films on a glass substrate using dithiols as linkers/mediators ( FIG. 8 ) (Wang et al., J. Phys. Chem. B 109:21593 (2005); Leibowitz et al., Anal. Chem. 71:5076 (1999); Luo et al., J. Phys. Chem. 108:9669 (2004), which are hereby incorporated by reference in their entirety).
- the dithiolate-gold binding chemistry involves a sequence of exchanging, crosslinking, and precipitation processes which has previously been demonstrated to occur to Au surface only. Thin film assemblies were observed for those with an Au surface, i.e., Fe 2 O 3 @Au ( FIG. 8 , (A)) and Au ( FIG. 8 , (B)) nanoparticles (or a combination of (A) and (B)). In contrast, there were no thin film assemblies for Fe 2 O 3 nanoparticles under the same reaction condition ( FIG. 8 , (C)).
- samples of the dithiol-mediated thin film assemblies of the nanoparticles were dissolved in aqua regia, and the composition was then analyzed using direct current plasma-atomic emission spectroscopy (DCP-AES) technique.
- the as-processed nanoparticles were also analyzed for comparison.
- 1,9-nonanedithiol-mediated assembly of nanoparticles into a thin film is selective to Au or Fe 2 O 3 @Au but not to Fe 2 O 3 .
- both Au and Fe were detected, demonstrating that the nanoparticles contain both Fe and Au components. It is therefore evident that the surface of Fe 2 O 3 particles must be covered by Au.
- the Au:Fe ratios for the thin films were slightly higher than those for the as-synthesized particles.
- the Au shell thickness can be estimated from the Au:Fe ratios based on a spherical core-shell model (Wang et al., J. Phys. Chem. B 109:21593 (2005), which is hereby incorporated by reference in its entirety).
- the results obtained from the DCP data for both the as-synthesized and the thin film (Table 1) are found to be very close to the values measured from the TEM data.
- FIGS. 9A-B show a representative set of SERS spectra for the core-shell Fe 2 O 3 @Au nanoparticles labeled with MBA.
- the SERS for Fe 2 O 3 @Au nanoparticles ( FIG. 9A ) showed clearly two peaks at 1084 and 1593 cm ⁇ 1 , which are identical to those observed for the Au nanoparticles ( FIG. 9B ).
- both the protein-binding properties of the gold shell and the magnetic properties of the core in the Fe 2 O 3 @Au nanoparticles are essential.
- the recent results of magnetic characterization for similar core-shell Fe-oxide Au nanoparticles have revealed detailed information for assessing the magnetic properties.
- FIGS. 10A-C a set of photos is shown to illustrate the movement of the nanoparticles dispersed in solutions before and after applying a magnetic field (NdFeB type) to the particles.
- the core-shell nanoparticles can be fully dispersed in toluene solution ( FIG. 10A ), which did not respond to external magnetic field of the magnet.
- FIG. 10B the suspension of the same nanoparticles in ethanol-toluene ( FIG. 10B ), which has an increased magnetic susceptibility due to aggregation, showed that the suspended particles moved towards the wall near the magnet gradually ( FIG. 10C ), eventually leaving a clear solution behind.
- FIG. 11A-B show a representative set of FTIR spectra of the OAM/OA-capped Fe 2 O 3 @Au nanoparticles before and after the ligand exchange reaction.
- the band at 3004 cm ⁇ 1 corresponding to the C—H stretching mode next to the double bond from OA and OM capping molecules ( FIG. 11A ) are clearly eliminated ( FIG. 11B ).
- the band at 1709 cm ⁇ 1 corresponding to the carboxylic acid group of MUA is detectable after the exchange reaction.
- the spectral change in the 1300-1560 cm ⁇ 1 region seemed to support the presence of bands corresponding to the symmetric and asymmetric stretching modes in the carboxylate groups of MUA.
- DSP protein-coupling agent
- Antibody anti-rabbit IgG was then immobilized onto the resulting nanoparticles via coupling with the surface DSP, forming Ab-immobilized core-shell nanoparticles.
- FIG. 12 illustrates the reactions and product separation of the antibody-labeled Fe 2 O 3 @Au nanoparticles in two different reaction systems: reaction with protein A capped gold nanoparticles (A1-B1), and reaction with BSA capped gold nanoparticles (A2-B2). In each case, magnetic field was applied to collect the magnetically-active products for SERS analysis.
- FIG. 13 shows a representative set of UV-Vis spectra monitoring the reaction progress. Results from control experiments are also included for comparison, in which the Au particles capped with BSA (bovine serum albumin) and MBA were used to replace the Au particles capped with protein A while maintaining the rest of the conditions.
- BSA bovine serum albumin
- MBA bovine serum albumin
- FIG. 14 shows a representative set of SERS spectra of the products collected by applying the magnet to the reaction solution for the Fe 2 O 3 @Au nanoparticles capped with anti-rabbit IgG and Au nanoparticles capped with protein-A.
- the spectrum from the control experiment is also included for comparison, in which the Au nanoparticles capped with BSA protein and MBA label were used to react with Fe 2 O 3 @Au nanoparticles capped with anti-rabbit IgG while maintaining the reaction conditions.
- Some of the major differences between the two nanoparticle products include the core-shell size range and the surface capping structure. Due to the unique processing environment, nanoparticles with much larger sizes can be made. The capping structure can be tailored differently in the two cases. These core@shell nanoparticles consist of magnetically-active Fe-oxide core and thiolate-active Au shell, which were shown to exhibit the Au surface binding properties for interfacial biological reactivity and the Fe-oxide core magnetism for magnetic bio-separation. These magnetic core-shell nanoparticles have therefore shown the viability for utilizing both the magnetic core and gold shell properties for interfacial bio-assay and magnetic bio-separation. These findings are entirely new, and could form the basis of fabricating size, magnetism, and surface tunable magnetic nanoparticles for bio-separation and biosensing applications.
Abstract
Description
TABLE 1 |
Analysis of Metal Composition in the |
Fe2O3@Au Nanoparticles |
Atomic | dshell (nm) | |||
ratio | determined by |
Sample | (Au:Fe) | TEM | DCP-AES | ||
As-synthesized | 77:23 | 1.1 | 1.0 | ||
Thin Film | 84:16 | 1.1 | 1.4 | ||
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US20180238868A1 (en) | 2018-08-23 |
US10006908B2 (en) | 2018-06-26 |
US20160231317A1 (en) | 2016-08-11 |
US20130071558A1 (en) | 2013-03-21 |
US10191042B2 (en) | 2019-01-29 |
US9327314B2 (en) | 2016-05-03 |
US20080226917A1 (en) | 2008-09-18 |
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